JP2015079885A - Metal wiring layer forming method, metal wiring layer forming apparatus, and storage medium - Google Patents

Abstract

A metal wiring layer can be formed in a recess of a substrate, and the metal wiring layer in the recess is not formed outside the recess.
In the metal wiring layer forming method, a catalyst layer 5 made of Pd is formed on a tungsten layer W provided on a bottom surface 3a of a recess 3 of a substrate 2, and a surface 3b of an insulating layer of the recess 3 is formed on the surface 3b. A step in which the catalyst layer 5 is not formed, and a step in which the Ni-based metal wiring layer 7 is formed on the catalyst layer 5 in the recess 3.
[Selection] Figure 2

Description

  The present invention relates to a metal wiring layer forming method, a metal wiring layer forming apparatus, and a storage medium for forming a metal wiring layer on a substrate.

  In recent years, semiconductor devices such as LSIs have been required to have higher density in order to cope with problems such as space saving of mounting area and improvement of processing speed. As an example of a technique for realizing high density, a multilayer wiring technique for manufacturing a multilayer substrate such as a three-dimensional LSI by stacking a plurality of wiring substrates is known.

  In the multilayer wiring technique, in general, in order to ensure conduction between wiring boards, a through via hole penetrating the wiring board and embedded with a conductive material such as copper (Cu) is provided in the wiring board.

  By the way, when manufacturing a wiring board, Cu is used as a conductive material and Cu is embedded in a concave portion of the substrate. In this case, a barrier film as a Cu diffusion prevention film is formed in the concave portion, and this barrier film is formed on the barrier film. It is necessary to form the seed film by electroless Cu plating. For this reason, the wiring volume of a wiring layer may fall or a void may generate | occur | produce in embedded Cu. On the other hand, a technique has been developed in which Ni-based metal is embedded in the recesses of the substrate instead of Cu by an electroless plating method and used as a wiring layer.

  However, when the Ni-based metal is embedded in the concave portion of the substrate, the Ni-based metal may be formed outside the concave portion, and in this case, the portion of the Ni-based metal formed outside the concave portion has a subsequent chemical structure. It must be removed using a mechanical polishing method.

JP 2010-185113 A

  The present invention has been made in consideration of the above points, and a metal wiring layer can be easily and easily formed in a recess of a substrate by plating, and the metal wiring layer formed in the recess is It is an object of the present invention to provide a metal wiring layer forming method, a metal wiring layer forming apparatus, and a storage medium that are not formed outside a recess.

  The present invention relates to a metal wiring layer forming method for forming a metal wiring layer on a substrate, a step of preparing a substrate having a recess including an insulating layer and having a tungsten layer formed on the bottom surface of the recess, and the insulating of the recess A step of forming a catalyst layer on the tungsten layer on the bottom surface of the recess without forming a catalyst layer on the surface of the layer, and a step of forming a metal wiring layer on the catalyst layer in the recess by plating. This is a method for forming a metal wiring layer.

  The present invention relates to a metal wiring layer forming method for forming a metal wiring layer on a substrate, the step of preparing a substrate having a recess including an insulating layer and having a tungsten layer formed on the bottom surface of the recess, And a step of bringing the coupling agent into the tungsten layer on the bottom without attaching the coupling agent to the surface of the insulating layer in the recess, and the coupling agent in the recess in the substrate. The step of forming the adhesion layer on the tungsten layer on the bottom surface of the recess without forming the adhesion layer on the surface of the insulating layer of the recess, and the tungsten on the bottom surface of the recess without forming the catalyst layer on the side surface of the recess A method of forming a metal wiring layer, comprising: forming a catalyst layer on the layer; and forming a metal wiring layer on the catalyst layer in the recess by plating.

  The present invention relates to a metal wiring layer forming apparatus for forming a metal line layer on a substrate, and has a recess including an insulating layer and a surface of the insulating layer in the recess with respect to the substrate having a tungsten layer formed on the bottom surface of the recess. Without forming a catalyst layer, a catalyst layer forming portion that forms a catalyst layer on the tungsten layer on the bottom surface of the recess, and a metal wiring layer forming portion that forms a metal wiring layer on the catalyst layer in the recess by plating A metal wiring layer forming apparatus.

  The present invention relates to a metal wiring layer forming apparatus for forming a metal line layer on a substrate, wherein the substrate has a recess including a bottom surface and a side surface and a tungsten layer is formed on the bottom surface of the recess. A silylating agent is added so that the coupling agent adheres to the tungsten layer on the bottom surface without attaching the coupling agent to the surface of the insulating layer in the recess, and the cup in the recess of the substrate. Without forming a contact layer on the side surface of the recess by applying a ring agent, an adhesion layer forming portion that forms an adhesion layer on the tungsten layer on the bottom surface of the recess, and without forming a catalyst layer on the side surface of the recess, A metal wiring comprising: a catalyst layer forming portion for forming a catalyst layer on the bottom tungsten layer; and a metal wiring layer forming portion for forming a metal wiring layer on the catalyst layer in the recess by plating. Layered It is a device.

  The present invention relates to a storage medium storing a computer program for causing a computer to execute a metal wiring layer forming method. The metal wiring layer forming method has a recess including a bottom surface and a side surface, and a tungsten layer is formed on the bottom surface of the recess. Preparing the formed substrate, forming the catalyst layer on the tungsten layer on the bottom surface of the recess without forming the catalyst layer on the side surface of the recess, and plating the metal wiring layer on the catalyst layer in the recess And a step of forming by processing.

  The present invention relates to a storage medium storing a computer program for causing a computer to execute a metal wiring layer forming method, wherein the metal wiring layer forming method has a recess including a bottom surface and a side surface, and a tungsten layer is formed on the bottom surface of the recess. And a step of providing a silylating agent in the recess of the substrate so that the coupling agent adheres to the tungsten layer on the bottom without attaching the coupling agent to the side of the recess; Forming a contact layer on the tungsten layer on the bottom surface of the recess and forming a catalyst layer on the side surface of the recess without applying a coupling agent in the recess of the substrate to form the contact layer on the side surface of the recess; And a step of forming a catalyst layer on the tungsten layer on the bottom surface of the recess, and a step of forming a metal wiring layer on the catalyst layer in the recess by plating. A storage medium characterized.

  According to the present invention, the metal wiring layer can be easily and easily formed in the recess of the substrate, and the formed metal wiring layer is not formed outside the recess.

FIG. 1 is a flowchart showing a metal wiring layer forming method according to the first embodiment of the present invention. FIG. 2 is a schematic diagram showing a metal wiring layer forming method according to the first embodiment of the present invention. FIGS. 3A to 3E are views showing a substrate on which the metal wiring layer forming method according to the first embodiment of the present invention is applied. FIG. 4 is a block diagram showing the metal wiring layer forming apparatus according to the first embodiment of the present invention. FIG. 5 is a flowchart showing a metal wiring layer forming method according to the second embodiment of the present invention. FIG. 6 is a block diagram showing a metal wiring layer forming apparatus according to the second embodiment of the present invention. FIG. 7 is a flowchart showing a metal wiring layer forming method as a comparative example. FIG. 8 is a schematic view showing a metal wiring layer forming method as a comparative example.

First Embodiment Hereinafter, a first embodiment of the present invention will be described with reference to FIGS.

  As shown in FIGS. 2A, 2B and 2C, the metal wiring layer forming method according to the present invention provides metal wiring to a silicon substrate 2 (hereinafter also referred to as a substrate) 2 made of a semiconductor wafer having a recess 3. The layer is formed.

  As shown in FIGS. 2A, 2B, and 2C, the substrate 2 has a recess 3 having a bottom surface 3a and a side surface 3b.

  In this case, the substrate 2 includes a substrate body 2a made of Si, a TEOS layer 2b formed on the substrate body 2a, a SiN layer 2c formed on the TEOS layer 2b, and a TEOS layer formed on the SiN layer 2c. 2d. A through hole is formed in the TEOS layer 2b, and a tungsten layer W is embedded in the through hole (see FIG. 2A).

  The above-described TEOS layer 2b, SiN layer 2c, and TEOS layer 2d are formed of an insulating layer.

  The substrate 2 having such a configuration can be obtained by a known method. For example, such a board | substrate 2 is obtained by the method shown to Fig.3 (a)-(e).

  First, a substrate 2 having a substrate body 2a made of Si is prepared (see FIG. 3A). Next, a TEOS layer 2b is formed on the substrate body 2a of the silicon substrate 2 by CVD, and a through hole 2e is formed in the TEOS layer 2b by etching (see FIG. 3B).

  Thereafter, as shown in FIG. 3C, a tungsten layer W is buried in the through hole 2e of the TEOS layer 2b by CVD.

  Next, as shown in FIG. 3D, the SiN layer 2c and the TEOS layer 2d are sequentially formed on the TEOS layer 2b and the tungsten layer W by CVD.

  Thereafter, the SiN layer 2c and the TEOS layer 2d on the tungsten layer W are removed by etching to obtain the substrate 2 in which the recess 3 including the insulating layer having the bottom surface 3a is formed (see FIG. 3E).

  In FIG. 3 (e), a recess 3 is formed in the substrate 2, and a tungsten layer W is formed on the bottom surface of the recess 3.

  Next, a metal wiring layer forming apparatus 10 that forms a metal wiring layer on the substrate 2 having the above-described recess 3 will be described with reference to FIG.

  Such a metal wiring layer forming apparatus 10 is provided in the subsequent stage of the oxide film removing unit 11 for removing the oxide film on the surface of the tungsten layer W on the bottom surface 3a of the recess 3 of the substrate 2 and the recess 3 Formation of the catalyst layer 5 (see FIGS. 2A, 2B, and 2C) on the tungsten layer W on the bottom surface 3a of the recess 3 without forming the catalyst layer 5 on the surface 3b of the insulating layer. Part 12 and a catalyst layer firing part 13 which is provided after the catalyst layer forming part 12 and which fires and hardens the catalyst layer 5. Further, a metal wiring layer forming part 14 for forming the metal wiring layer 7 on the catalyst layer 5 in the recess 3 by a plating process is provided downstream of the catalyst layer baking part 13.

  Each component of the metal wiring layer forming apparatus 10 described above, for example, the oxide film removing unit 11, the catalyst layer forming unit 12, the catalyst layer firing unit 13, and the metal wiring layer forming unit 14 are all provided in the control device 20. Drive control is performed by the control device 20 in accordance with various programs recorded in the storage medium 21, whereby various processes are performed on the substrate 2. Here, the storage medium 21 stores various setting data and various programs such as a metal wiring layer forming program described later. As the storage medium 21, known media such as a computer-readable memory such as ROM and RAM, and a disk-shaped storage medium such as a hard disk, CD-ROM, DVD-ROM, and flexible disk can be used.

  Next, the operation of the present embodiment having such a configuration will be described with reference to FIGS.

  As described above, in the previous step shown in FIGS. 3A to 3E, the recess 3 is formed on the substrate (silicon substrate) 2 made of a semiconductor wafer or the like, and the substrate 2 on which the recess 3 is formed is the present invention. Is transferred into the metal wiring layer forming apparatus 10. In this case, the substrate 2 includes a substrate body 2a made of Si, a TEOS layer 2b, a SiN layer 2c, and a TEOS layer 2d. The substrate 2 is formed with a recess 3 including an insulating layer having a bottom surface 3a. Yes.

  And the tungsten layer W is formed in the bottom face 3a of the recessed part 3 of the board | substrate 2 (refer Fig.2 (a)).

  Here, as a method of forming the recess 3 in the substrate 2, a conventionally known method can be adopted as appropriate. Specifically, for example, as a dry etching technique, a general-purpose technique using a fluorine-based or chlorine-based gas or the like can be applied. In particular, a hole having a large aspect ratio (hole depth / hole diameter) is formed. Can adopt the method which adopted the technique of ICP-RIE (Inductively Coupled Plasma Reactive Ion Etching: Inductively Coupled Plasma-Reactive Ion Etching) capable of high-speed deep etching, more particularly, sulfur hexafluoride ( A method called a Bosch process in which an etching step using SF6) and a protection step using a Teflon-based gas such as C4F8 are repeated can be suitably employed.

  Next, in the metal wiring layer forming apparatus 10, the substrate 2 having the recesses 3 as shown in FIG. 1 is sent to the oxide film removing unit 11, where the recesses are formed by a cleaning process using a DHF solution. 3 is removed. The oxide film on the surface of the tungsten layer W formed on the bottom surface 3a is removed.

  Next, the substrate 2 is sent to the catalyst layer forming portion 12, and in this catalyst layer forming portion 12, the tungsten layer formed on the bottom surface 3 a of the recess 3 without forming the catalyst layer 5 on the surface 3 b of the insulating layer of the recess 3. The catalyst layer 5 is formed only on the W surface (see FIG. 2B).

  As described above, in the oxide film removing unit 11 provided in the front stage of the catalyst layer forming unit 12, the oxide film on the surface of the tungsten layer W formed on the bottom surface 3a of the recess 3 of the substrate 2 is cleaned using the DHF solution. Is removed. In this case, the adhesion layer forming step using the coupling agent on the recess 3 and the periphery thereof is not performed on the substrate 2 sent from the oxide film removing unit 11 to the catalyst layer forming unit 12. On the other hand, in the oxide film removing portion 11, the oxide film on the tungsten layer W formed on the bottom surface 3 a of the recess 3 is removed.

  As described above, since the surface 3b of the insulating layer of the recess 3 is mainly formed of an insulating layer composed of the SiN layer 2c and the TEOS layer 2d, the insulating layer of the recess 3 is formed in the catalyst layer forming portion 12 unless an adhesion layer is formed. The catalyst layer 5 is not formed on the surface 3b. For this reason, in the catalyst layer forming part 12, the catalyst layer is formed only on the tungsten layer W from which the oxide film has been removed from the surface.

  Next, the catalyst forming step in the catalyst layer forming unit 12 will be further described.

  As shown in FIG. 2B, in the catalyst formation step, for example, a process of spraying an aqueous palladium chloride solution onto the substrate 2 with a nozzle and adsorbing Pd ions as a catalyst onto the surface of the substrate 2 is adopted. Can do. Specifically, a tin chloride solution is sprayed on the substrate 2 to adsorb tin ions on the surface of the substrate 2, and then an aqueous palladium chloride solution is sprayed on the substrate 2 to replace the tin ions with Pd ions, thereby replacing the Pd ions. Further, sodium hydroxide is sprayed onto the substrate 2 to remove excess tin ions. Thus, the catalyst layer 5 can be provided only on the tungsten layer W formed on the bottom surface 3 a of the recess 3 of the substrate 2.

  Or when forming the catalyst layer 5 on the tungsten layer W of the recessed part 3 of the board | substrate 2, you may use the catalyst solution containing the catalyst which has a catalytic action which can accelerate | stimulate a plating reaction, for example, the catalyst which consists of nanoparticles. Here, the nanoparticle is a particle having a catalytic action and having an average particle diameter of 20 nm or less, for example, in the range of 0.5 nm to 20 nm. Examples of the elements constituting the nanoparticles include palladium, gold, and platinum.

  Moreover, ruthenium may be used as an element constituting the nanoparticles.

  The method for measuring the average particle size of the nanoparticles is not particularly limited, and various methods can be used. For example, when measuring the average particle diameter of the nanoparticles in the catalyst solution, a dynamic light scattering method or the like can be used. The dynamic light scattering method is a method for calculating the average particle diameter of the nanoparticles by irradiating the nanoparticles dispersed in the catalyst solution with laser light and observing the scattered light. Further, when measuring the average particle size of the nanoparticles adsorbed on the recess 3 of the substrate 2, a predetermined number of nanoparticles, for example, 20 nanoparticles, are detected from an image obtained using a TEM or SEM. The average value of the particle diameters of these nanoparticles can also be calculated.

  Next, a catalyst solution containing a catalyst composed of nanoparticles will be described. The catalyst solution contains metal ions that constitute the nanoparticles that serve as the catalyst. For example, when the nanoparticles are composed of palladium, the catalyst solution contains a palladium compound such as palladium chloride as a palladium ion source.

  The specific composition of the catalyst solution is not particularly limited, but preferably the composition of the catalyst solution is set so that the viscosity coefficient of the catalyst solution is 0.01 Pa · s or less. By setting the viscosity coefficient of the catalyst solution within the above range, the catalyst solution can be sufficiently distributed to the bottom surface 3a of the recess 3 of the substrate 2 even when the diameter of the recess 3 of the substrate 2 is small. As a result, the catalyst can be more reliably adsorbed to the bottom surface 3 a of the recess 3 of the substrate 2.

  Preferably, the catalyst in the catalyst solution is coated with a dispersant. Thereby, the interfacial energy at the catalyst interface can be reduced. Therefore, the diffusion of the catalyst in the catalyst solution can be further promoted, and it is considered that the catalyst can reach the bottom surface 3a of the recess 3 of the substrate 2 in a shorter time. In addition, it is possible to prevent a plurality of catalysts from aggregating and increasing their particle size, and it is considered that the diffusion of the catalyst in the catalyst solution can be further promoted.

  The method for preparing the catalyst coated with the dispersant is not particularly limited. For example, a catalyst solution containing a catalyst previously coated with a dispersant may be used.

  Specifically, as the dispersant, polyvinyl pyrrolidone (PVP), polyacrylic acid (PAA), polyethyleneimine (PEI), tetramethylammonium (TMA), citric acid and the like are preferable.

  In addition, various chemicals for adjusting the characteristics may be added to the catalyst solution.

  Thus, in the catalyst layer forming part 12, the catalyst layer 5 is formed only on the surface of the tungsten layer W formed on the bottom surface 3a of the recess 3.

  The substrate 2 having the catalyst layer 5 formed on the surface of the tungsten layer W in this manner is sent to the catalyst layer firing unit 13, and the substrate 2 is heated in the catalyst layer firing unit 13. Thus, the catalyst layer 5 on the surface of the tungsten layer W formed on the bottom surface 3a of the recess 3 is baked and hardened.

  When the catalyst layer 5 is formed of metal nanoparticles, the catalyst layer 5 can be hardened more effectively by firing the catalyst layer 5.

  Next, the substrate 2 is sent from the catalyst layer baking unit 13 to the metal wiring layer forming unit 14. In the metal wiring layer forming portion 14, for example, an electroless NiB plating solution is supplied into the concave portion 3 of the substrate 2 to perform a plating process, and thus the electroless layer 5 on the tungsten layer W is electrolessly treated. A metal wiring layer 7 made of a NiB plating layer is formed.

  In the present embodiment, the metal wiring layer 7 formed on the catalyst layer 5 may be a metal wiring layer 7 made of Ni, NiB, NiP, Co, CoB, CoP, or the like.

  As described above, according to the present embodiment, the catalyst layer 5 is formed only on the surface of the tungsten layer W provided on the bottom surface 3a of the recess 3 of the substrate 2, and the catalyst layer is formed on the surface 3b of the insulating layer of the recess 3. Since 5 is not formed, the metal wiring layer 7 can be provided only in the recess 3. In this case, the metal wiring layer 7 is not formed outside the recess 3, and therefore the metal wiring layer 7 formed outside the recess 3 does not need to be removed by chemical mechanical polishing.

  Next, a metal wiring layer forming method as a comparative example will be described with reference to FIGS.

  In the comparative example shown in FIGS. 7 and 8, first, a substrate 2 having a recess 3 including a bottom surface 3a is prepared (see FIG. 8A). In this case, a tungsten layer W is provided on the bottom surface 3 a of the recess 3.

  Next, the substrate 2 is subjected to a hydroxylation treatment including a plasma treatment, and the bottom surface 3a of the recess 3 and the surface 3b of the insulating layer are hydroxylated.

  Next, a silane coupling agent is applied to the bottom surface 3a (tungsten layer W) of the recess 3 of the substrate 2 and the surface 3b of the insulating layer to form an adhesion layer on the bottom surface 3a of the recess 3 and the surface 3b of the insulating layer. A catalyst layer made of Pd is formed on the adhesion layer (see FIG. 8B). In FIG. 8B, the adhesion layer and the catalyst layer on the substrate 2 are indicated by reference numeral 8.

  Thereafter, as shown in FIG. 8C, the substrate 2 is plated, and the metal wiring layer 7 made of, for example, an electroless NiB plating layer is formed in the recess 3. In the comparative example shown in FIG. 8C, the adhesion layer and the catalyst layer 8 are also formed on the bottom 3a of the recess 3 of the substrate 2 and the surface 3b of the insulating layer. Formed.

  For this reason, in FIG.8 (c), it is necessary to remove the part formed in the outward of the recessed part 3 of the board | substrate 2 among the metal wiring layers 7 by chemical mechanical polishing.

  On the other hand, according to the present embodiment, since the catalyst layer 5 is provided only on the surface of the tungsten layer W provided on the bottom surface of the recess 3 of the substrate 2, the metal wiring layer 7 formed on the catalyst layer 5 is recessed. 3 can be stopped. For this reason, after forming the metal wiring layer 7 in the recess 3, the step of removing the metal wiring layer 7 formed outside the recess 3 by chemical mechanical polishing can be eliminated.

  For this reason, the metal wiring layer forming process can be simplified and made efficient.

Second Embodiment Next, a second embodiment of the present invention will be described with reference to FIGS.

  The metal wiring layer forming apparatus 10 according to the second embodiment shown in FIGS. 5 and 6 includes an oxide film removing unit 11 that removes an oxide film on the surface of the tungsten layer W, and a catalyst layer forming unit 12 that forms a catalyst layer 12. A silylating agent providing unit 16 and an adhesion layer forming unit 17 are provided between the first and second embodiments, and other configurations are substantially the same as those of the first embodiment shown in FIGS.

  In the second embodiment shown in FIG. 5 and FIG. 6, the same parts as those in the first embodiment shown in FIG. 1 to FIG.

  In the second embodiment shown in FIGS. 5 and 6, the silylating agent providing unit 16 provides a silylating agent in the recess 3 of the substrate 2, and a cup described later on the surface 3 b of the insulating layer of the recess 3. The ring agent does not adhere, and the coupling agent adheres only to the surface of the tungsten layer W on the bottom surface 3a. Further, the adhesion layer forming portion 17 does not form a adhesion layer on the surface 3b of the insulating layer of the recess 3 by applying a coupling agent in the recess 3 of the substrate 2, but only on the tungsten layer W on the bottom surface 3a. To form.

  Next, the operation of the present embodiment having such a configuration will be described. In the metal wiring layer forming apparatus 10, as shown in FIG. 5, the substrate 2 having the recess 3 (see FIG. 2A) is sent to the oxide film removing unit 11, where the DHF solution The oxide film on the surface of the tungsten layer W formed on the bottom surface 3a of the concave portion 3 is removed by the cleaning process using. At the same time, the surface 3b made of the insulating layer of the recess 3 is hydroxylated.

  Next, the substrate 2 is sent to the silylating agent providing unit 16, where the silylating agent is applied to the substrate 2. Such a silylating agent may be TMSDMA.

  By applying the silylating agent to the substrate 2 in this manner, the hydroxyl group is removed on the surface 3b of the insulating layer of the recess 3 so that the surface 3b of the insulating layer does not adhere to the silane coupling agent described later. be able to.

  At this time, a hydroxyl group remains on the tungsten layer W formed on the bottom surface 3 a of the recess 3, and the silane coupling agent is maintained on the tungsten layer W.

  Next, the substrate 2 is sent to the adhesion layer forming unit 17, and a coupling agent such as a silane coupling agent is applied to the substrate 2 in the adhesion layer forming unit 17. At this time, the surface 3b of the insulating layer of the recess 3 is in a state in which the silane coupling agent is difficult to adhere because the hydroxyl group is removed. On the other hand, since the tungsten layer W formed on the bottom surface 3a of the recess 3 maintains a state in which the silane coupling agent adheres, the silane coupling agent is applied only on the tungsten layer W formed on the bottom surface 3a of the recess 3. Adhere to.

  Note that, before the substrate 2 to which the silylating agent is applied in the silylating agent applying unit 16 is sent to the adhesion layer forming unit 17, the substrate 2 may be heated to heat the tungsten layer W. In this case, the silane coupling agent can be reliably applied on the tungsten layer W in the adhesion layer forming portion 17.

  Next, the operation of the adhesion layer forming unit 17 will be further described.

  The adhesion layer forming unit 17 has a vacuum chamber (not shown) having a heating unit, and in this adhesion layer forming unit 17, a coupling agent such as a silane coupling agent is adsorbed on the substrate 2 having the recess 3. Thus, an adhesion layer is formed on the tungsten layer W formed on the bottom surface 3a of the recess 3 (SAM treatment). The adhesion layer formed by adsorbing the silane coupling agent improves the adhesion with the catalyst layer 5 described later.

  The substrate 2 on which the adhesion layer is formed in the adhesion layer forming unit 17 is sent to the catalyst layer forming unit 12. In the catalyst layer forming unit 12, for example, Pd ions serving as a catalyst are adsorbed on the adhesion layer of the substrate 2 to form the catalyst layer 5 (see FIG. 2B).

  In this case, since the adhesion layer of the substrate 2 is provided only on the tungsten layer W formed on the bottom surface 3 a of the recess 3, the catalyst layer 5 is also formed only on the tungsten layer W formed on the bottom surface 3 a of the recess 3. Thus, the catalyst layer 5 is not formed on the surface 3 b of the insulating layer of the recess 3.

  Thus, in the catalyst layer forming part 12, the catalyst layer 5 is formed only on the surface of the tungsten layer W formed on the bottom surface 3a of the recess 3.

  The substrate 2 having the catalyst layer 5 formed on the surface of the tungsten layer W in this manner is sent to the catalyst layer firing unit 13, and the substrate 2 is heated in the catalyst layer firing unit 13. Thus, the catalyst layer 5 on the surface of the tungsten layer W formed on the bottom surface 3a of the recess 3 is baked and hardened.

  When the catalyst layer 5 is formed of metal nanoparticles, the catalyst layer 5 can be hardened more effectively by firing the catalyst layer 5.

  Next, the substrate 2 is sent from the catalyst layer baking unit 13 to the metal wiring layer forming unit 14. In the metal wiring layer forming portion 14, for example, an electroless NiB plating solution is supplied into the recess 3 of the substrate 2 to perform a plating process, and thus the electroless NiB is formed on the catalyst layer 5 on the tungsten layer W. A metal wiring layer 7 made of a plating layer is formed.

  In the present embodiment, the metal wiring layer 7 formed on the catalyst layer 5 may be a metal wiring layer 7 made of Ni, NiB, NiP, Co, CoB, CoP, or the like.

  As described above, according to the present embodiment, the catalyst layer 5 is formed only on the surface of the tungsten layer W provided on the bottom surface 3a of the recess 3 of the substrate 2, and the catalyst layer is formed on the surface 3b of the insulating layer of the recess 3. Since 5 is not formed, the metal wiring layer 7 can be provided only in the recess 3. In this case, the metal wiring layer 7 is not formed outside the recess 3, and therefore the metal wiring layer 7 formed outside the recess 3 does not need to be removed by chemical mechanical polishing.

2 Substrate 3 Recess 3a Bottom 3b Surface 5 Catalyst layer 7 Metal wiring layer 10 Metal wiring layer forming apparatus 11 Oxide film removing unit 12 Catalyst layer forming unit 13 Catalyst layer firing unit 14 Metal wiring layer forming unit 16 Silylating agent applying unit 17 Adhesion Layer forming unit 20 Controller 21 Storage medium W Tungsten layer

Claims (16)

In a metal wiring layer forming method for forming a metal wiring layer on a substrate,
Preparing a substrate having a recess including an insulating layer and having a tungsten layer formed on the bottom surface of the recess;
Forming a catalyst layer on the tungsten layer on the bottom surface of the recess without forming the catalyst layer on the surface of the insulating layer of the recess; and
And a step of forming a metal wiring layer on the catalyst layer in the recess by plating.   2. The oxide film on the surface of the tungsten layer is removed without forming an adhesion layer on the bottom surface of the recess and the surface of the insulating layer before forming the catalyst layer on the tungsten layer on the bottom surface of the recess. The metal wiring layer formation method of description.   3. The method for forming a metal wiring layer according to claim 1, wherein the catalyst layer is fired and hardened after the catalyst layer is formed on the tungsten layer on the bottom surface of the recess.   4. The method for forming a metal wiring layer according to claim 1, wherein the catalyst layer is made of a palladium-based catalyst layer, and the metal wiring layer is made of a Ni-based wiring layer. In a metal wiring layer forming method for forming a metal wiring layer on a substrate,
Preparing a substrate having a recess including an insulating layer and having a tungsten layer formed on the bottom surface of the recess;
A step of providing a silylating agent in the recess of the substrate, and allowing the coupling agent to adhere to the bottom tungsten layer without attaching the coupling agent to the surface of the insulating layer of the recess;
A step of forming an adhesion layer on the tungsten layer on the bottom surface of the recess without applying a coupling agent in the recess of the substrate and forming an adhesion layer on the surface of the insulating layer of the recess;
Forming a catalyst layer on the tungsten layer on the bottom surface of the recess without forming the catalyst layer on the side surface of the recess;
And a step of forming a metal wiring layer on the catalyst layer in the recess by plating.   6. The method for forming a metal wiring layer according to claim 5, wherein the oxide film on the surface of the tungsten layer is removed before applying the silylating agent in the recess of the substrate.   7. The metal wiring layer forming method according to claim 5, wherein the catalyst layer is fired and hardened after the catalyst layer is formed on the tungsten layer on the bottom surface of the recess.   8. The method of forming a metal wiring layer according to claim 5, wherein the catalyst layer is made of a palladium-based catalyst layer, and the metal wiring layer is made of a Ni-based wiring layer. In a metal wiring layer forming apparatus for forming a metal line layer on a substrate,
A catalyst layer is formed on the tungsten layer on the bottom surface of the recess without forming the catalyst layer on the surface of the insulating layer in the recess with respect to the substrate having the recess including the insulating layer and the tungsten layer formed on the bottom surface of the recess. A catalyst layer forming part to perform,
A metal wiring layer forming apparatus, comprising: a metal wiring layer forming portion that forms a metal wiring layer on a catalyst layer in a recess by plating.   10. The metal wiring layer forming apparatus according to claim 9, wherein an oxide film removing unit for removing an oxide film on the surface of the tungsten layer is provided in front of the catalyst layer forming unit.   The metal wiring layer forming apparatus according to claim 9 or 10, wherein a catalyst layer firing part for firing and solidifying the catalyst layer is provided between the catalyst layer forming part and the metal wiring layer forming part. In a metal wiring layer forming apparatus for forming a metal line layer on a substrate,
For a substrate having a recess including a bottom surface and a side surface and having a tungsten layer formed on the bottom surface of the recess, a silylating agent is applied in the recess of the substrate, and the coupling agent adheres to the surface of the insulating layer of the recess. A silylating agent-providing portion for allowing the coupling agent to adhere to the bottom tungsten layer without
An adhesion layer forming portion that forms an adhesion layer on the tungsten layer on the bottom surface of the recess without applying a coupling agent in the recess of the substrate and forming an adhesion layer on the side surface of the recess;
Without forming a catalyst layer on the side surface of the recess, a catalyst layer forming portion that forms a catalyst layer on the tungsten layer on the bottom surface of the recess;
A metal wiring layer forming apparatus, comprising: a metal wiring layer forming portion that forms a metal wiring layer on the catalyst layer in the recess by plating.   13. The metal wiring layer forming apparatus according to claim 12, wherein an oxide film removing unit for removing an oxide film on the surface of the tungsten layer is provided before the silylating agent providing unit.   14. The metal wiring layer forming apparatus according to claim 12 or 13, wherein a catalyst layer firing part for firing and solidifying the catalyst layer is provided between the catalyst layer forming part and the metal wiring layer forming part. In a storage medium storing a computer program for causing a computer to execute a metal wiring layer forming method,
The metal wiring layer forming method is
Preparing a substrate having a recess including a bottom surface and a side surface, and having a tungsten layer formed on the bottom surface of the recess;
Forming a catalyst layer on the tungsten layer on the bottom surface of the recess without forming the catalyst layer on the side surface of the recess;
And a step of forming a metal wiring layer on the catalyst layer in the recess by plating. In a storage medium storing a computer program for causing a computer to execute a metal wiring layer forming method,
The metal wiring layer forming method is
Preparing a substrate having a recess including a bottom surface and a side surface and having a tungsten layer formed on the bottom surface of the recess;
A step of providing a silylating agent in the concave portion of the substrate, so that the coupling agent adheres to the tungsten layer on the bottom surface without adhering the coupling agent to the side surface of the concave portion, and
Forming a contact layer on the tungsten layer on the bottom surface of the recess without applying a coupling agent in the recess of the substrate and forming the contact layer on the side surface of the recess;
Forming a catalyst layer on the tungsten layer on the bottom surface of the recess without forming the catalyst layer on the side surface of the recess;
And a step of forming a metal wiring layer on the catalyst layer in the recess by plating.

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